EP0005230B1 - Liant pour matières de revêtement pulvérulentes - Google Patents

Liant pour matières de revêtement pulvérulentes Download PDF

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Publication number
EP0005230B1
EP0005230B1 EP79101231A EP79101231A EP0005230B1 EP 0005230 B1 EP0005230 B1 EP 0005230B1 EP 79101231 A EP79101231 A EP 79101231A EP 79101231 A EP79101231 A EP 79101231A EP 0005230 B1 EP0005230 B1 EP 0005230B1
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Prior art keywords
acid
weight
groups
oxide
und
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EP0005230A3 (en
EP0005230A2 (fr
Inventor
Eckhard Dr. De Cleur
Rolf Dr. Dhein
Hans Dr. Rudolph
Hans Joachim Dr. Kreuder
Hanns Peter Dr. Müller
Walter Dr. Schäfer
Kuno Dr. Wagner
Kurt Dr. Findeisen
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/20—Compositions for powder coatings

Definitions

  • the present invention relates to powdered coating compositions which contain a uretonimine or polyuretonimine as the crosslinking component.
  • Binders for powdered coating compositions generally consist essentially of an oligomer or polymer with functional groups as the first component and a crosslinking agent which reacts with the functional groups of the oligomer or polymer under baking conditions as the second component.
  • Powdery coating compositions which contain blocked polyisocyanates as crosslinking agents have long been known (DE-AS 1 957 483, 2 064 C98, 2 215 080). These blocked polyisocyanates have the advantage, at room temperature and slightly elevated temperature, of not reacting with the reactive groups of the first component, as desired, but rapidly releasing the blocking agent under baking conditions and then reacting with the first component to provide the crosslinking function intended for them fulfill.
  • a peculiarity of the electrostatic powder spraying process is that in some places (on horizontal surfaces, in corners and angles) thicker layers are formed than on the rest of the substrate. However, as soon as the layer thickness exceeds a limit value - generally 120-150 ⁇ m - surface defects occur at these points when baked. One therefore frequently encounters the phenomenon that an object, which is generally excellently coated, has a varnish - mostly blistered - in some places.
  • the present invention had u. a. Overcoming the prejudice that uretonimines or polyuretonimines would not be suitable as powder coating crosslinkers because of a premature reaction.
  • a polyisocyanate preferably a diisocyanate
  • a carbodiimide or polycarbodiimide preferably an isocyanate group-containing carbodiimide or polycarbodiimide with itself, with the formation of products containing uretonimine groups, the uretonimine groups themselves reacting again as new reactive groups with the component to be crosslinked can kick.
  • the binders according to the invention prove to be surprisingly stable in storage.
  • a binder containing hydroxyl groups when stored for more than 8 weeks at 40 ° C and even when compounding in the extruder no noticeable crosslinking.
  • Preferred crosslinkers (b) contain these percentages each refer to the weight of the crosslinking agent (b).
  • Uretonimines are known; they are accessible by 2 + 2 cycloaddition of isocyanates onto carbodiimides (DE-PS 1 012 601, DE-AS 1 568 501, DE-OS 2 504 400, 2 523 586, 2 537 685, 2 552 340, 2 552 350 ; Angew. Chem. 74, 801 [1962]; J. Organ. Chem. 33, 1913 [1968]; J. Elastoplastics 4, 259 (1972]).
  • any isocyanates can be added to carbodiimides.
  • the blocking of carbodiimides containing isocyanate groups with itself ie. H. with the carbodiimide groups of the next molecule.
  • This mostly preferred variant naturally requires that the mostly catalytic carbodiimidization reaction of the polyisocyanates is stopped in good time before all the free isocyanate groups have reacted.
  • aromatic polyisocyanates this is e.g. Currently often associated with difficulties, so that they are not very suitable for sole use in the production of the uretonimines to be used according to the invention:
  • the conversion of isocyanates to carbodiimides is known (DE-OS 2 245 634, 504 400, 2 556 760, 2 624198, US Pat. No. 2,663,737, 2,663,738, 2,663,739, 2,853,473 and 2,941,966).
  • the reaction can be terminated - in particular in the case of non-aromatic isocyanates - in principle by cooling or by converting the catalyst to a catalytically inactive reaction product.
  • the risk that the crosslinking agents will continue to condense and release carbon dioxide when mixing the powder coating components in the extruder can be countered by adding carbodimidization a temperature that is 20-40 ° C above the melt temperature of the extruder, until the carbon dioxide elimination has essentially ended.
  • the uretonimines are formed from the isocyanate group-containing carbodiimides or isocyanate / carbodiimide mixtures mostly spontaneously during cooling; Copper salts have a catalytic effect on this ring formation.
  • Uretonimines or polyuretonimines can therefore generally be prepared by reacting organic polyisocyanates, preferably diisocyanates, optionally in the presence of 0.001-5% by weight, based on polyisocyanate, of a carbodiimidization catalyst at a temperature between 80 and 220 ° C lets until 40 to 90% of the isocyanate groups have been reacted (verification of the amount of carbon dioxide developed) and the reaction product by cooling, if appropriate in the presence of 0.05 to 1% by weight, based on free isocyanate groups, of a ring-forming catalyst into the corresponding Uretonimine or polyurethane imine transferred. .
  • Alicyclic isocyanates such as. B. 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, cyclohexane-1,4-diisocyanate 4,4'-diisocyanato-dicyclohexylmethane, 2,4- and 2,6-diiocyanato-1- methylcyclohexane mixture (ratio 80:20).
  • Hexamethylene diisocyanate, 2,2,4- and 2,4,4-trimethythexamethylene diisocyanate, oxadiazinetrione groups and / or uretdione groups, diisocyanates containing biuret or isocyanurate groups on hexamethylene diisocyanate and 1-isocyanato-3,3,5-trimethyl are also very suitable -5-isacyanatomethyl-cyclohexane base, as well as mixtures thereof.
  • Mixtures consisting of aliphatic or cycloaliphatic isocyanates and up to 30 mol% aromatic diisocyanates can also be used to prepare the uretonimines to be used according to the invention.
  • modified isocyanates e.g. As glycol, diglycol, polyether, polycarbonates or polyester, the production of further variants of the uretonimines to be used according to the invention.
  • zerewitinoffactive compounds which react faster with isocyanate groups than with carbodiimide and uretonimine groups or monoisocyanates can also be added before, during or after the carbodiimidization in minor amounts.
  • Preferred zerewitinoffactive compounds are e.g. As methanol, ethanol, cyclohexanol, phenol, mercaptan, aniline, 1,2,4-triazole, e-caprolactam, pyrrolidone, malonate and ethyl acetoacetate.
  • monoisocyanates such.
  • uretonimines to be used according to the invention, e.g. B.
  • the diisocyanates optionally together with a small amount of zerewitinoffactive compounds or with monoisocyanates (ratio of zerewitinoffactive compounds or monoisocyanates to diisocyanates ⁇ 1) in the presence of a carbodiimidization catalyst heated to temperatures of 80-250 ° C to 40-90% of the isocyanate groups are converted to carbodiimide groups with evolution of carbon dioxide, whereupon the carbodiimidization is terminated by cooling to room temperature.
  • a carbodiimidization catalyst heated to temperatures of 80-250 ° C to 40-90% of the isocyanate groups are converted to carbodiimide groups with evolution of carbon dioxide, whereupon the carbodiimidization is terminated by cooling to room temperature.
  • the amount of carbon dioxide generated during carbodiimidization which can be easily measured with the help of a gas meter, is equivalent to the theoretical carbodiimide content.
  • the difference between it and the uretonimine content gives the real carbodiimide content.
  • the uretonimine content of the products according to the invention can be calculated from the difference in the isocyanate contents, namely determined once at room temperature and once at 180 ° C.
  • the isocyanate content is determined on the basis of the consumption of di-n-butylamine.
  • a carbodiimidization catalyst is a mixture of 1-methyl-1-phospha-2-cyclopentene-1-oxide and 1-methyl-1-phospha-3-cyclopentene-1-oxide, which is generally present in amounts of 0.1-5% by weight % is added to the isocyanate, preferred.
  • the reaction temperature is generally 80__180 ° C.
  • the preparation of the crosslinking agents to be used according to the invention is preferably carried out in the melt, but can also be carried out in a solvent such as. B. toluene, xylene or decalin, the solvent being removed after the reaction by suitable methods.
  • An advantage is that, starting from one and the same isocyanate, the melting point can be varied within a wide range, depending on the requirements and the extent of the carbodiimidization.
  • the uretonimines to be used according to the invention can be ground or pulverized and can be distributed homogeneously in this form in the reactants.
  • a great advantage is that the polyisocyanatocarbodiimide addition products to be used according to the invention are reactive powders which can undergo defined crosslinking reactions with reactants and thereby release no or only a few blocking agents.
  • Compounds can be used as reaction partners (a). carry the functional groups, which react with uretonimine, carbodiimide and isocyanate groups depending on the reaction temperature, e.g. B. hydroxy, carboxyl, mercapto, amino, amide, urethane and (thio) urea groups.
  • Polymers, polycondensates and polyaddition compounds can be used as polymers (a).
  • Preferred components (a) are primarily polyethers, polythioethers, polyacetals, polyamides, Polyesteramides, epoxy resins with hydroxyl groups in the molecule, phenoi / formaldehyde resins, aminoplasts and their modification products with polyfunctional alcohols, aniline / formaldehyde resins, polyazomethines, polyurethanes, polyureas and pofythioureas, polysulfonamides, melamine derivatives, cellulose esters and ethers, and partly verse Copolymers of vinyl esters, partially acetalized polyvinyl alcohols, but especially polyesters and acrylate resins.
  • the hydroxyl group-containing polymers to be used primarily the hydroxyl number is generally between 20 and 400, preferably between 30 and 140 mg KOH / g.
  • Preferred potyesters are e.g. B. also the reaction products of polycarboxylic acids and glycidyl compounds, as z. B. are described in DE-OS 2 410 513.
  • glycidyl compounds that can be used are esters of 2,3-epoxy-1-propanol with monobasic acids that have 4 to 18 carbon atoms, such as glycidyl palmitate, glycidyl laurate and glycidyl stearate; Alkylene oxides with 4 to 18 carbon atoms, such as butylene oxide, and glycidyl ethers, such as octyl glycidyl ether.
  • the polyesters can be obtained in a manner known per se by condensation in an inert gas atmosphere at temperatures of 100-260 ° C., preferably 130-220 ° C., in the melt or in an azeotropic procedure, as described, for. B. in methods of organic chemistry (Houben-Weyl), Vol. 14/2, 1-5, 21-23, 40-44, Georg Thieme Ver! Ag, Stuttgart, 1963 or at CR Martens Alkyd Resins, 51-59 , Reinhold Plastics Appl. Series, Reinhold Publishing Comp., New York, 1961.
  • Preferred polycarbonates are those which, for. B. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol, tetraethylene glycol with diaryl carbonates, e.g. B. diphenyl carbonate or phosgene can be produced.
  • diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6)
  • diethylene glycol triethylene glycol
  • tetraethylene glycol e.g. B. diphenyl carbonate or phosgene
  • the acrylate resins can be prepared by the customary methods, that is to say by solution, suspension, emulsion or precipitation polymerization; but preferably by substance polymerization, which in turn can be initiated by means of UV light.
  • the usual peroxides or azo compounds such as. B. dibenzoyl peroxide, tert-butyl perbenzoate, or azodiisobutyronitrile.
  • the Molekularq e -wicht can for. B. with sulfur compounds, Wigert-dodecyl mercaptan, can be regulated.
  • Preferred polyethers (a) have at least two, usually two to eight, preferably up to three, hydroxyl groups and can, for.
  • epoxides such as ethylene, propylene oxide, butylene oxide, trimethylene oxide, 3-bis (chloromethyl) oxacyclobutane, tetrahydrofuran, styrene oxide, the bis (2,3-epoxypropyl) ether of diphenylolpropane or epichlorohydrin with itself, e.g. B. in the presence of BF 3 , or by the addition of these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms, such as water, ammonia, alcohols or amines, for. B.
  • reactive hydrogen atoms such as water, ammonia, alcohols or amines
  • Suci osepoly decisivher as z. B. described in DE-AS 1 176 358 and 1 064 938, are suitable as component (a).
  • those polyethers are preferred which predominantly (up to 90% by weight, based on all the OH groups present in the polyether) have primary OH groups.
  • polyethers such as z. B. by polymerization of styrene, acrylonitrile in the presence of polyethers (US Pat. Nos. 3,383,351, 3,304,273, 3,523,093, 3,110,695, DE-PS 1,152,536) are also suitable, as are OH groups Polybutadienes.
  • Preferred components (a) are also polyacetals, e.g. B. from glycols, such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldimethylmethane, hexanediol and formaldehyde available compounds (also by polymerization of cyclic acetals, suitable polyacetals can be prepared), in particular also polyoxymethylenes, for. B.
  • glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldimethylmethane, hexanediol and formaldehyde available compounds (also by polymerization of cyclic acetals, suitable polyacetals can be prepared), in particular also polyoxymethylenes, for. B.
  • copolymers of formaldehyde or trioxane with 1,3-dioxolane, 1,3-oxthiolane or ethylene oxide such as cane sugar, invert sugar, starch, dextrin, cellulose and their alkylation, acylation, transesterification and degradation products; spirocyclic polyacetals from pentaerythritol and glyoxal.
  • phenol / formaldehyde resins e.g. B. those which can be obtained by the customary methods, especially in the presence of excess formaldehyde, from phenol, tert-butylphenol, cresols, xylenols, resorcinol or diphenylolalkanes by acidic or alkaline condensation, and their cyanethylation and hydrogenation products.
  • hydroxyl-containing polyurethanes and / or polyureas with average molecular weights of 400 to 15,000 can be used.
  • thiodiglycol and the condensation products of thiodiglycol with itself and / or with other glycols, cicarboxylic acids, formaldehyde, amino carboxylic acids or amino alcohols (depending on the co-components, the products are polythio ether, polythio ether ester, polythio ether ester amide) .
  • polymer captals in particular those made from formaldehyde and 1,4-tetramethylene dimercaptan or 1,6-hexamethylene dimercaptan.
  • Preferred compounds (a) containing amino groups are: polyarnines such as hexamethylene diamine, melamine, melamine / formaldehyde condensates, ⁇ , ⁇ -diaminocaproic acid esters with lower (C 1 -C 17 ) fatty alcohols, the toluenediamines, optionally substituted diphenylmethane diamines, their homologues, hydrogenation products of the aromatic Di- and polyamines, aminocaproic acid, polydmid polyamines, which, for. B.
  • polyimides containing terminal amino groups such as, for. B. poly-dibenzimidazoles and polyimides from pyromellitic anhydride and diamines and the known modification products of polyphosphononitrile chlorides with polyamines.
  • Preferred components (a) are e.g. B. also polyamines, e.g. B. polyethyleneimines, their cyanethylation and hydroxyalkylation products, in particular reaction products of polyalkylene polyamines with epichlorohydrin, furthermore the hydrogenation products of cyanethylated high molecular weight polyamines and polyalcohols, aniline / formaldehyde resins, and also polyether alcohols or polyesters. It is also possible to use polyesteramides and polyamides as reactants a) for the uretonimines, e.g. B.
  • gelatin or casein furthermore also polyester amides from the polycarboxylic acids mentioned, polyalcohols and polyamines or from polycarboxylic acids and amino alcohols such as ethanolamine, 4-aminobutanol-1, 6-aminohexanol-1, diethanolamine or aminophenols.
  • Further preferred components (a) are the condensation products known as polyhydrazides from dicarboxylic acids and hydrazine, the methylene polyamides from dinitriles and formaldehyde and the polysulfonamides, for. B. from n-hexane-1,6-bis-sulfonic acid chloride or m-benzene-bis-sulfonic acid chloride and 1,6-hexamethylene diamine.
  • aminoplast resins e.g. B. based on urea, thiourea, melamine, dicyandiamide, hexamethylene diurea, ethylene urea, acetylene urea or m-benzenedisulfonamide, and their modification products with polyols.
  • polyureas e.g. B from hexamethylene diamine or bis (y-aminopropyl) ether by condensation with carbon dioxide, urea or diphenyl carbonate, from 1,10-decamethylene diamine by condensation with 1,6-hexamethylene-bisethyl urethane or by polyaddition of diamines such as 4,4'- Diaminodiphenylmethane, 4,4'-diaminodiphenyl, 1,8-octamethy lendiamine, 2,6-diaminotoluene-4-sulfonic acid sodium, on polyisocyanates such as 1,6-hexamethylene diisocyanate, 2,4-tolylene diisocyanate or 4,4'-diisocyanatodiphenylmethane; Polythioureas, e.g.
  • B from hexamethylenediamine or p-xylylenediamine by condensation with carbon disulfide or trithiocarbonic acid esters or by polyaddition of diamines to disene oils, e.g. B. Hexamethylene iron oil.
  • polyurethanes e.g. B. from low molecular weight mono- or polyalcohols, such as ethylene glycol, propylene glycol, butanediol, Hexandio l, diethylene glycol, triethylene glycol, thiodiglycol, N, N-di- (t 3-hydroxyethyl) aniline or m-toluidine, N-methyldiethanolamine, hydroquinone di ( ⁇ -hydroxyethyl) ether, adipic acid di ( ⁇ -hydroxyethyl) ester, N, N, N ', N'-tetra (2-hydroxypropyl) ethylenediamine, glycerol, trimethylolpropane, mannitol or glucose , by polyaddition to polyisocyanates such as hexamethylene diisocyanate, tetramethylene diisocyanate, tolylene diisocyanate, p-phenylene diiso
  • bis-chloroformates such as ethylene glycol bis-chloroformates or butanediol-1,4-bis-chloroformates
  • di- or polyamines such as ethylenediamine, hexamethylenediamine, bis- (3- ) ether, piperazine, 1,4-diaminocyclohexane, bis- (4-amino-3-methylpheny
  • polymers in which subsequent treatment, for. B. by a grafting reaction or by hydrolysis process against isocyanates functional groups include polyvinyl alcohol, anverseiftes polyvinyl acetate, anverseiftes polyvinyl acetate-polyethylene copolymer, anverseifte polyacrylic ester, anverseifte Polyvinylidencarbonate, hydrogenation products of ethylene-carbon monoxide copolymers, graft polymers of vinyl compounds such as vinyl chloride, vinyl acetate or acrylonitrile, a linear or branched polyethers, polyacetals or polymers of the type mentioned which contain functional groups with respect to isocyanates.
  • the listed components a) are of course only suitable as a binder base if they have at least two groups per molecule which are reactive with the isocyanate or uretonimine group.
  • the combination of the polyisocyanatocarbodiimide addition products b) compounds a), in particular with polyhydroxyl compounds, can be treated with Hoze for coatings for metals, wood, fabrics, plastics, as a hot melt adhesive or with fillers such as powdered metals such. As aluminum, bronze, copper, iron, zinc, use as a metal substitute.
  • fillers can also be mixed in, such as plastic powder, for example polyethylene, polypropylene, polyacrylonitrile-polybutadiene-polystyrene, natural and synthetic rubbers; Waste rubber; Minerals, e.g. B. pumice, alumina, garnet, quartz, feldspar or other abrasive materials; Silicates, e.g.
  • Metal oxides e.g. B. iron oxide, zinc oxide, titanium oxide, magnesium oxide, ferrites, e.g. B. zinc ferrite
  • metal sulfides e.g. B iron sulfide, zinc sulfide, lead sulfide
  • various solid fillers such as graphite, carbon black pigments, glass fibers and metal fibers.
  • Derfr auxiliaries in the powdered binders according to the invention include pigments and fillers and substances for improving the flow and for avoiding surface defects, such as e.g. B. silicone oils, p-toluenesulfonic acid amide, liquid acrylate resins and plasticizers and catalysts.
  • Suitable catalysts are, for example, tin compounds such as di-n-butyltin oxide, di-n-butyltin dialkyl ester or titanium acid esters, in particular tetraisopropyl titanate.
  • the softening points of the binders according to the invention are generally such that they can be processed at temperatures between 80 and 120 ° C. with the additives necessary for the preparation of the coating compositions according to the invention.
  • The. Softening points of the mixtures are such that the binders according to the invention can be ground to form non-clumping, free-flowing powders with a particle size of about 20 to about 120 u. In practice, this means that the polymers used have softening points between about 40 and about 200 ° C.
  • the powdery coating agents can in suitable mixing units, for. B in stirred tanks or mixing screws (extruders), and are processed into powders which are applied in a conventional manner, in particular according to the electrostatic powder spray process (EPS process) Documents are applied.
  • EPS process electrostatic powder spray process
  • the coating films cure quickly by heating to temperatures above 130 ° C, preferably between about 150 and 220 ° C, to hard and smooth coatings.
  • the melting points of the substances of Examples 1-14 were measured in a capillary in a melting point determination apparatus according to Dr. Tottoli determined.
  • 168 g of hexamethylene diisocyanate are mixed with 0.4 ml of a mixture of 1-methyl-1-phospha-2-cyclopenten-1-oxide and 1-methyl-1-phospha-3-cyclopenten-1-oxide.
  • the mixture is heated to 180 ° C. until 12 liters of carbon dioxide have formed within 40 minutes and then poured onto a metal sheet, where it solidifies to a grindable mass.
  • the necessary components - 85 g of a branched terephthalate polyester of terephthalic acid, neopentyl glycol, hexanediol and trimethylolpropane (1.5% OH) and 15 g of crosslinking agent from Example 1 - are premixed together with 40 g of titanium dioxide as a pigment in finely divided form.
  • a commercially available copolymer of butyl acrylate and 2-ethylhexyl acrylate is used as leveling agent (1-2%, based on binder).
  • the leveling agent is incorporated in the form of a so-called master batch, i.e. H. 100 parts of the polyester are melted with 10 parts of the leveling agent and comminuted after solidification.
  • the mixture is homogenized on a commercially available twin-screw, self-cleaning extruder device.
  • the jacket temperature is chosen so that the outlet temperature of the melt is approximately 125 ° C.
  • the melt cake can be left to its own devices, or on the other hand, as is usual in practice, it can be rapidly cooled using a continuously operating squeezing and cooling device. After cooling down to temperatures of 20-30 C, it is roughly pre-ground and then finely ground with fan cooling. The resulting fine-particle powder is then freed from coarser particles above a particle size of approx. 0.09 mm by air sifting or by mechanical sieving
  • the test with the water results in a tough and elastic chip and confirms the excellent adhesion in the cross-cut test method.
  • the solvent resistance indicates good chemical crosslinking.
  • the varnishes are resistant to toluene, ethyl glycol acetate and acetone with a contact time of several minutes until the surface first softens. The coating does not dissolve A 2 ) Preparation of crosslinkers
  • the softening points of the substances of Examples 16-24 were determined by means of differential thermal analysis.
  • a weighed amount of the product is heated in chlorobenzene for a few minutes to determine the isocyanate content, a clear solution is obtained which, after cooling to room temperature, is mixed with di-n-butylamine in order to determine the isocyanate groups by titrimetry.
  • the NCO content is 13% .
  • compositions are prepared according to the following table, which are intimately mixed on a pan mill:
  • the grain fraction ⁇ 90 ym is applied to degreased iron sheets using an electrostatic spray system at a voltage of 60 kV and baked at 200 ° C for 15 minutes.
  • a polyacrylate resin prepared according to DE-OS 2 600 318 made from 30 parts of styrene, 36 parts of methyl methacrylate, 20 parts of butyl acrylate, 13 parts of hydroxypropyl methacrylate and 1 part of acrylic acid (resin index: hydroxyl number: 50; acid number: 10; molecular weight M w : 20,000; M n : 10,000); Softening point approx. 60 ° C (DME) are processed with -15 parts of crosslinking component according to Example 19 and 1 part of leveling agent analogously to Example 15, as described in Examples 26 and 27, to an unpigmented powdery coating agent and applied to degreased metal sheets, then for 30 minutes. Baked at 200 ° C. The resulting clear coats are hard and resistant to acetone.
  • DE-OS 2 600 318 Softening point approx. 60 ° C

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Claims (5)

1. Agent liant pour agents de revêtement pulvérulents, consistant en
(a) 25 à 95% en poids d'au moins un monomère, oligomère ou polymère contenant des groupes hydroxyle, uréthane, carboxyle, mercapto, amino, amide, urée ou thiourée et ayant une température de transition vitreuse entre 40 et 200°C (mesurée par analyse différentielle thermique) et
fb) 5 à 75% en poids d'au moins un polyisocyanate bloqué ayant un point cie fusion entre 40 et 220° C, 'es indications de pourcentages de (a) et de (b) formant en tout chaque fois 100,
caractérisé en ce que le réticulant (b) contient au moins un groupe urétonimine par molécule.
2 Agent liant selon la revendication 1, caractérisé en ce qu'il consiste en
50 a 95% en poids de composant a et en
50 a 5% en poids de composant b.
3 Agent liant selon l'une quelconque des revendications 1 et 2, caractérisé en ce que le composant b possède un point de fusion entre 60 et 180° C.
4. Agent liant selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le composant b contient
0,5-35% en poids de groupes urétonimine,
0-27% en poids de groupes isocyanate libres et
0-30% en poids de groupes carbodiimide.
5. Agent liant selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le composant b contient
0,5 - 26% en poids de groupes urétonimine,
0-27% en poids de groupes isocyanate libres et
0-27% en poids de groupes carbodiimide.
EP79101231A 1978-05-05 1979-04-24 Liant pour matières de revêtement pulvérulentes Expired EP0005230B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2819827 1978-05-05
DE19782819827 DE2819827A1 (de) 1978-05-05 1978-05-05 Pulverfoermige ueberzugsmittel

Publications (3)

Publication Number Publication Date
EP0005230A2 EP0005230A2 (fr) 1979-11-14
EP0005230A3 EP0005230A3 (en) 1979-11-28
EP0005230B1 true EP0005230B1 (fr) 1981-05-20

Family

ID=6038773

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79101231A Expired EP0005230B1 (fr) 1978-05-05 1979-04-24 Liant pour matières de revêtement pulvérulentes

Country Status (9)

Country Link
US (1) US4248978A (fr)
EP (1) EP0005230B1 (fr)
JP (1) JPS54146832A (fr)
AT (1) AT377995B (fr)
CA (1) CA1133181A (fr)
DE (2) DE2819827A1 (fr)
DK (1) DK185279A (fr)
ES (1) ES480245A1 (fr)
ZA (1) ZA792147B (fr)

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DE2943469A1 (de) * 1979-10-27 1981-05-07 Bayer Ag Pulverfoermige beschichtungsmaterialien
US4430489A (en) 1982-04-28 1984-02-07 Thiokol Corporation One-package, heat-curable sealant compositions comprising a blocked polyisocyanate and a blocked polyamine
EP0161854B1 (fr) * 1984-04-29 1988-11-02 Nitto Electric Industrial Co., Ltd. Méthode d'assemblage d'un alliage et d'une plaque métallique avec une composition de résine
DE3609687A1 (de) * 1985-03-29 1986-10-02 Nisshinbo Industries, Inc., Tokio/Tokyo Duroplastisches harz und verfahren zu seiner erzeugung
DE3600766A1 (de) * 1986-01-14 1987-07-16 Bayer Ag Verfahren zur herstellung von carbodiimidgruppen enthaltenden, blockierten polyisocyanaten, die nach diesem verfahren erhaeltlichen polyisocyanate und deren verwendung zur herstellung von polyurethankunststoffen
CH677995B5 (fr) * 1986-01-31 1992-01-31 Inventa Ag
DE3714033A1 (de) * 1987-04-28 1988-11-17 Bayer Ag Lackbindemittel, ihre verwendung in beschichtungsmitteln und ein verfahren zur herstellung von drahtlackierungen
GB8712577D0 (en) * 1987-05-28 1987-07-01 Ici Plc Coating compositions
DE3718238A1 (de) * 1987-05-30 1988-12-15 Bayer Ag Lackbindemittel, ihre verwendung in beschichtungsmitteln, ein verfahren zur herstellung von drahtlackierungen und eine lackschicht aufweisende hitzeresistente substrate
US5112931A (en) * 1989-07-17 1992-05-12 Miles Inc. Blocked polyisocyanates for the production of powder coatings with flat finishes
US5051464A (en) * 1989-09-01 1991-09-24 E. I. Du Pont De Nemours And Company Waterborne acrylourethane pigment dispersant polymer
DE4018184A1 (de) * 1990-06-07 1991-12-12 Bayer Ag Verfahren zur stabilisierung von estergruppen enthaltenden kunststoffen
DE4022660A1 (de) * 1990-07-17 1992-01-23 Bayer Ag Bindemittelkombination, ihre verwendung in einbrennlacken und ein verfahren zur herstellung von ueberzuegen
US5371148A (en) * 1993-06-23 1994-12-06 Union Carbide Chemicals & Plastics Technology Corporation Reactive polymers having pendant flexible side chains prepared from ethylenically unsaturated carbodiimides
JPH09157588A (ja) * 1995-10-04 1997-06-17 Nisshinbo Ind Inc ウレタン系塗料用硬化剤及びポリエステル／ウレタン系塗料
JPH10316893A (ja) * 1997-05-16 1998-12-02 Tomoegawa Paper Co Ltd 耐熱性粉体塗料
JP7342388B2 (ja) * 2019-03-15 2023-09-12 富士フイルムビジネスイノベーション株式会社 粉体塗料、塗装品、及び、筆記ボード
EP3730528A1 (fr) 2019-04-24 2020-10-28 Covestro Deutschland AG Préparations adhésives à réaction latente

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US3168483A (en) * 1961-01-17 1965-02-02 Air Prod & Chem Diazabicyclooctane-alkylene oxide catalyst compositions
US3214412A (en) * 1962-08-23 1965-10-26 Du Pont 1, 2-bis(dialkylamino)-1, 2-diisocyanato-ethylenes and n, n'-bis(alpha-fluorodialkyl-aminomethyl) uretidine diones
DE1571136A1 (de) * 1964-07-09 1970-08-13 Elastomer Ag Verfahren zur Oberflaechenbeschichtung mit Polyurethanen im Spruehverfahren
GB1147383A (en) * 1965-07-13 1969-04-02 Ici Ltd Polymeric compositions
US3489744A (en) * 1966-07-18 1970-01-13 Uniroyal Inc Preparation of diisocyanate dimers in aqueous medium
US3564041A (en) * 1967-04-26 1971-02-16 Upjohn Co 1,2,3-trihydrocarbylguanidine-1-carboxylates
DE2312391A1 (de) * 1973-03-13 1974-09-19 Bayer Ag Pulverfoermige, vernetzbare ueberzugsmittel
DE2420475A1 (de) * 1974-04-27 1975-11-06 Bayer Ag Uretdiongruppen aufweisende polyadditionsprodukte
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JPS52124027A (en) * 1976-04-12 1977-10-18 Hitachi Ltd Thermosetting powder coatings

Also Published As

Publication number Publication date
DE2819827A1 (de) 1979-11-08
EP0005230A3 (en) 1979-11-28
ES480245A1 (es) 1980-08-16
AT377995B (de) 1985-05-28
ZA792147B (en) 1980-06-25
JPS54146832A (en) 1979-11-16
EP0005230A2 (fr) 1979-11-14
US4248978A (en) 1981-02-03
ATA331579A (de) 1984-10-15
CA1133181A (fr) 1982-10-05
DK185279A (da) 1979-11-06
DE2960366D1 (de) 1981-08-27

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